Hydrogenation of phenol-ketone



Patented May 31 1938 2,113,954v

UNITED STATES PATENT "OFFICE HYDROGENATION or rnnNoL-Ka'romt CONDENSATION raonvc'rs Raymond E. Thomas, Newburgh, N. Y., assignor to E. I. du 'Pont de Nemours & Comp Wilmington, Del, a corporation of Delaware No Drawln8- Application Mai-ch19, lass.

. Serial No. 69,867

l6 Claims. (01. zoo -1'53) This invention relates to a process for comdisclosed by Jordan in U. S.--1 ,59 3,081, and the, pletely hydrogenating 'phenol-ketone condensaclose resemblance of the above 2-methy1-4-iso-' tion products and to the production of certain propyl cyclohexanol to the compound (boiling new and useful products. u i point 108-112 C./12 mm.) obtained by Jordan It has heretofore been proposed to hydrogenate leads to the conclusion that they are identical. 5 phe'nol-ketone condensation products employing It follows, therefore, that there has been disas catalysts nickel, colloidal palladium, or platicovered a new process which yields hitherto num black, the reaction beingicarriedout under unknown compositions of matter.

I pressure, in the absence of a solvent, and at This invention has as an object the preparatemperatures varying between 50 and 170 C. tion ofcompletely hydrogenated phenol-ketone Thus, in U. S. 1,593,081, issued July 20, 1926, condensation products. A further object is the to Jordan, it is disclosed that di(4-hydroxy-3- development of a process for. catalytically hydromethyl-phenyl) dimethylmethane may be comgenating phenol-ketonecondensation products to pletely hydrogenated by reacting the same with the corresponding completely saturated materials hydrogen under pressure at 150 C.-to 170 C., without cleavage of the starting material. A 15 and in the presence of 2 to 5' parts of nickel still further object is the preparationoi' certain catalyst. From this reaction Jordan obtained new anduseiul compositions of matter. Other di(4-hydroxy-3-methylcyclohexanyl) dimethylobjects will. appear hereinafter. methane, which is described as a viscous, limpid The above and other objects appearing hereoil boiling at 108-112 (31/12 mm. and having a inafter are accomplished by charging a soluvery agreeable scent resembling that .of hyation'oi the phenol-ketone condensationproduct;

cinths. in two or three times its weight 01 a suitable.

It has been found that hydrogenation of 1,1- solvent, e. g.,"ethanol, into an autoclave equipped di(4-hydroxy-3-methylphenyl) dimethylmethane with an eflicient stirrer and built to, withstand 2 under pressure at 180 to 200 C. in the presence high pressures and temperatures, adding about 2 of a nickel catalyst and a solvent, e. g., ethanol, 10 to 20% of nickel catalyst, based on theweight produces an entirely different product; My prod-, of the material to be hydrogenated, and hydro--' not is .an odorless, semi-solid, plastic material genating at elevated temperatures and preshaving a boiling point of 180-190 C./2 mm. comsures. I v

- prising a number of isomers that are diflicult The following. examples are to be taken as to separate. Similar results are obtained with illustrative and not as limiting the invention. 1,1-di(4-hydroxyphenyl)dimethylmethane,- ex'- gamble I cept that pure isomers may be isolated readily I by fractional crystallization. The physical and Forty-six hundred grams of di(4-hydroxychemical properties of the product obtained by phenyl) dimethylmethaneare dissolved in 12,000 35 hydrogenating dl-(4-hydroxy-3-methylphenyl) grams of absolute ethanol and the solution dlmethyhnethane characterize it as di(4-hycharged into ahlgh pressure autoclave. together droxy 3 -methylcyclohexanyl) dimethylmethane, witl; 800 grams of a nickel-on-kieselguhr hydroand since these properties are not those-of Jorgen tion catalyst. Themixture is stirred, treated 40 dans product we believe that Jordan erred in with hydrogen at pressures ranging from 1500 40 calling his product dl(4-hydroxy-3-methylcycloto 2500 pounds per square inch, and heated to hexanyD-dimethylmethane. Further evidence to a maximum temperature of 200 'C. Under substantiate this belief is ofiered by an example these conditions hydrogen .is absorbed rapidly;

. in British 254,753 '(complete acceptance 8/9/28), beginning at a temperature of 180 0., and the issued to Chemische Fabrik aus Aktien, in which reaction is continued until no more hydrogen is 4 di(4-hydroxy-3-methylphenyl)dimethylmethane absorbed. The solution is removed from the was hydrogenated in an autoclave under pressure autoclave, filtered to remove the catalyst, and at 160 to 180 C. in the presence of a hydrogenatthe solvent removed by distillation. The resulting catalyst. From this reaction two products ing product is, treated with small portions of s were isolated and identified as 2-methyl cyclohot 5% aqueous'sodium' hydroxide solution until -50 hexane] and 2-methyl-4-isopropyl cyclohexanol, all alkali-soluble material is removed, and then boiling point 1 l2-115 0.112 .mm. These prodwashed with hot water until the washings are" ucts resulted from. the cleavage of the starting neutral to phenolphthalein. The crude hydro- 1 material and subsequent hydrogenation-of the genated di(4-hydroxyphenyl)dimethylmethane fragments. -The similarity of this process to that is a white, semi-solid, plastic mass, soluble in 55 y the mixture having thane is well known,

alcohol but insoluble inwater and alkalis, B. P. 180-210 C./2 mm., consisting of a mixture of geometric isomers. By fractional crystallization first from alcolfol-benzene mixtures and then from acetone, the product is separated into three fractions as follows;

One thousand grams of a pure solid isomer, M. R. 187-189 C.; 1500 grams of a mixture of solid isomers, M. R. 140l60 C4 and 1200grams of mixed liquid isomers. The crude products also be purified by fractional distillation, a boiling point of 175-200 C./2 mm.

The hydrogenated di(4 -hydroxyphenyl)dimethylmethane corresponds in its properties to di( 4 hydroxycyclohexanyl) dimethylmethane which is represented by the Analysis of the solid portion gives the following values: Calculated for C15H2802; carbon, hydrogen 11.67%. Found (high melting isomer) Carbon 74.96%; hydrogen 11.54; (mixed solid isomers) carbon 75.36; hydrogen 11.64. The presence of two secondary hydroxyls in the molecule is indicated by catalytic dehydrogenation over a selective dehydrogenation catalyst in accordance with the process described in the U. S. application by Wilbur A. Lazier, Serial No. 67,305

filed March 5, 1936 and issued as U. 5. Patent No. 2,088,425 on July 27, 1937, whereby exactly two mols of hydrogen are liberated from each mol. of compound "treated. The structural formula of di(4-hydroxyphenyl) dimethylmeand this, in combination with the above facts is evidence: for the foregoing structural formula for hydrogenated di(4-hy droxyphenyl)dimethylmethane. No evidence of the presence of hydrogenated cleavage products of di(4 hydroxphenyl) dimethylmethane is found under the conditions of this experiment.

" sam le 11 uct similar to that of Example I was obtained.

Example III A I, Thirteen hundred grams of di(4hydroxy-3- methylphenyl) dimethylmethane are dissolved in 2600 grams of ethanol and the solution charged into a high pressure autoclave together with 250 grams of a nickel-on-ki'eselguhr cata-, lyst. The mixture isstirred, treated with hydrogen at pressures ran from 2500 to 3000 pounds heated-to a maximum of per square inch and 200 C. Beginning at 18in C. the hydrogen abreaction is continued sorption is very rapid; the until no more hydrogen is taken up. The crude hydrogenated di(4-hydroxy.-1i-methylphenyl)di- Y (5 ingsolution to remove methylmethane is isolated by filtering the resultthe catalyst, and distilling following structural a pressure ranging off the solvent. The residual product is washed repeatedly with small portions of hot 5% sodium I point of 180-195 C./1 mm. This product has the structure: me n H, H, H on,

- CH: V no-c c-on it i. v A. it

' Example IV A nickel hydrogenating catalyst is prepared according to the following procedure:

Five hundred and eighty grams of crystalline nickel nitrate are dissolved in 2,000 grams of distilled water, and 200 grams of finely. divided kieselguhr added. The mixture is continuously stirred at a rate just suiiicient to keep the kieselguhr and subsequent precipitate in suspension, and heated to 65 to 70 C. A 3.5% solution of sodium carbonate is then added through spray nozzles so placed as to deliver a fine mist-like spray uniformly over the surface of the mixture at the rate of 750 grams of solution per hour. Addition of the carbonate is continued until a filtered sample of the mother liquor has a pH of 7.6 -to 7.8. Addition of precipitant is then stopped, and the mixture allowed to cool and settle. After decanting the mother liquor, the precipitate is washed at room temperature five times by decantation, each wash consisting of a volume of 0.15% ammonium carbonate'solution equal to the volume of liquor decanted. The precipitate is then filtered and dried at a temperature not exceeding C.

The product thus formed, which consists of basic nickel carbonate supported on kieselguhr, is very soft and crumbles easily to an extremely finely divided powder. It contains 30% nickel,

size, preferably inclined at an angle of about 45, and equipped with aslowly 'moving spiral agitator. The furnace is then heated at 450- 500 C. while passing hydrogen through at the rate .of 500cc. per gram of catalyst per hour. After four to six hours reduction, the catalyst is cooled to room temperature in hydrogen flowing at a diminished rate. A catalyst so prepared contains 25 to 29% elementary nickel which represents 85 to 95% of the total available nickel.

. Seventy-five grams of 1,1-di(4-hydroxyphenyl) cyclohexane is dissolved in grams of ethanol,

the solution mixed with 15 grams of nickel-onture, pressure, concentration, duration of re- .tially the addition of 12 atoms'of hydrogen to kieselguhr catalyst, and the mixture charged into Filtercel, pumice, or magnesia. A typical method a high pressure autoclave. The mixture is'stirred, of preparing a supported catalyst is described in treated with hydrogen under pressures ranging Example III. In general, a reduced nickel catafrom 1500 to 2500 pounds per square inch, and lyst supported on kieselguhr is preferred in the heated to a maximum temperature of 200 C. practice of this invention.

The absorption of hydrogen begins at 190 C. and The phenol-ketone condensation products of the reaction is continued until no more hydrogen this invention are generally prepared by reactis taken up. The solution is discharged from the ing substantially two mols of the phenol with subautoclave, filtered to remove the catalyst, and stantially one moi. of the ketone in the presence the product, 1,1-di(4-hydroxycyclohexanyl) cyof a suitable condensing agent, e. g., hydrochloric l0 clohexane, recovered as a mixture of solid isoor sulfuric acids. The condensation products mers (melting point 220-240 C.) by crystallizathus obtained have the general formula:

tion from alcohol. Further crystallization from H H H 3, alcohol yields 5 grams of a pure solid isomer, I I R A 6 1 M. R. 238240 C., and 48.4 grams of a mixture of g T 15 solid isomers, M. R. 220-230 C. The latter prodnot is insoluble in water and alkalis, and only 1;, Q- C/ moderately soluble in organic solvents; catalytic t l l dehydrogenation thereof yields 2 mols of -hydrogen per mol. of product treated. Its properties Where R d R1 may be ke or unlike alkyl or 20 correspond with the following structural forgroups, and wherein or more m; I drocarbon radicals may be substituted for hydrogen atoms joined directly to either of the aro- 1 A J 5 matic nuclei. Compounds coming within the P f I scope of this type formula include the di(4-hy- 5 HO-C 0- 0 6 43-011 droxyphenyl) dimethylmethane, di 4-hydroxy-3- methylphenyl) dimethylmethane, and 1,1-di(4- I I 5 I hydroxyphenyl) cyclohexane of the examples, and others such as 1,1-di(4-hydroxyphenyl)4- c .tertiary-amyl-cyclohexane, di(4-hydroxynaphm thylldimethyimethane, 2,2-di(4-hydrox yphenyl) decahydronaphthalene, 1,1-di(4-hydroxyphenyl). Although in the above examples there is in- 3,5-dirnethyl cyclohexane, and the like. dicated certain definite conditions of tempera- The process of this invention comprises .essenaction, catalyst and the. like, it is to be underthe aromatic nuclei of compounds represented stood that these values may be varied, since the by the above type formula, in accordance with specific conditions in any one case are determined the following equation:

c-c t. 0-0 m i ct z 1i r'r :-o H {I Ill 7 '1 Ha Hi i H: 1 i v v 45 both by the nature of the catalyst and by the ma- Among the compounds produced in this way terial treated. from phenol-ketone condensation products may Broadly, the process of this invention is opbe mentioned di'(4-hydroxycyclohexany) dimetherable within the temperature range from apylmethane, 1,1-di(ri-hydroxycyclohexanyl) cyclo- 5 proximately 175 to 250 C. and at pressures ranghexane, 'di(4-hydroxy-'3-methyl cyclohexanyl)diing from atmospheric to a maximum determethylmethane, 2,2-di(4-hydroxycyclohexanyl)- mined by the practical limitations of the equipdecahydronaphthalene, and the like. ment employed. It is preferable, however, to This invention utilizes economicaland highly use temperatures from appr ximately 80 Q. o eflicient catalytic processes in the production of 210 C., and pressures from 100t0 200 atmosa large numberofuseful, but hitherto unavail- 55 pheres. The most rapid absorption of hydrogen able compounds. The process operates at moderoccurs between 190 and 200 C. ate temperatures and pressures, and under these The use of a solvent in the practice of this conditions hydrogenated phe'nol-ketone condennv nt on i of ia impor ance. since he sation products are formed in unusually high formation of hydrogenated cleavage products 8 yields with a minimum of undesirable cleavage 60 thereby avoided even at high temperatures. Alproducts. The hydrogenated products are isothough ethers, alcohols, or hydrocarbons may be lated readily in the pure state by the method des the C o c o e pecific solvent is deterscribed in the examples. These products are of mined n c Case by the ub y of the comparticular interest as intermediates in the prepa- (15 p und d- A o ol Su as t ano ration of polyhydric alcohol-polycarboxylic acid ethanol and butanol, and others such as dioxan resins, etc., for the preparation of plasticizers, Y are generally preferred. wax blending agents, coating compositions, in-

The catalysts of this invention include those secticides, and the like. These compounds'are Catalysts 0f the Eighth oup f th d c also useful as modifying agents for lubricating 7 Ta e w c a commonly wn as y oge a oils, as gasoline antioxidants, and in the manuing metals. I These include nickel, platinum, and facture of rubber compositions. The specific palladium, and they are. employed in an exuses for a given hydrogenated phenol-ketone tremely fine state of subdivision, either in the condensation product are determined to a conmassive state or supported on suitable inert masiderable extent by the properties and structure terials such as kieselguhr, activated charcoal, of the compound. 75

Since many widely different embodiments of this invention may be made without departing from the spirit or scope thereof, it is to be understood that wedo not limit ourselves to the speciiic embodiments thereof except as defined in the following claims.

I claim: k

1. A process for catalytically hydrogenating phenol-ketone condensation products which comprises reacting the phenol-ketone condensation product, dissolved in an organic solvent. with hydrogen in the presence of a hydrogenating catalyst at a temperature within the range of 175 to 250 C. and at elevated pressures.

2. The process in accordance with claim 1 characterized in that the temperature is within the range of 180-200 C.

3. The process in accordance with claim 1 characterized in that the pressure is within the range of -200 atmospheres.

4. The process in accordance with claim 1 characterized in that the organic solvent is selected from the class consisting of alcohols, ethers, and hydrocarbons.

5. The process in accordance with claim 1 characterized in that the catalyst is a hydrogenating metal selected from the elements of the Eighth Group of the Periodic Table.

6. The process in accordance with claim 1 characterized in that the reaction is carried out in the presence of a nickel-on-kieselguhr catalyst characterized in that the phenol-ketone condensation product is di(4-hydroxyphenyl)dimethylmethane.

8. The process in accordance with claim 1 characterized in that the phenol-ketone condensation product is di(4-hydroxy-3-methylphenyl) dimethylmethane.

9. The process in accordance with claim 1 characterized in that the phenol-ketone condensation product is 1,1-di(4-hydroxyphenyl)cyclohexane.

10. The process of catalytically hydrogenating phenol-ketone condensation products which comprises bringing di(4-hydroxyphenyl) dimethylmethane, dissolved in approximately three times its weight of ethanol, into contact with hydrogen in the presence or nickel-on-kieselguhr hydrogenating catalyst at a temperature withinthe range of ISO-200 C. and under a pressure of 100-200 atmospheres.

11. The process or catalytically hyd ogenating a phenol-ketone condensation product which comprises bringing (11(4 hydroxy 3 methylphenyl) dimethylmethane, dissolved in approximately twice its weight of ethanol, into contact with hydrogen in the presence of a nickel-onkieselguhr hydrogenating catalyst at a temperature within the range or ISO-280 0., and under a pressure. of approximately 100-200 atmospheres.

- 12. The process of catalytically hydrogenating a phenol-ketone condensation product which comprises bringing 1,1 di(4 hydroxyphenyl) 7: The process in accordance with claim 1 cyclohexane, dissolved in approximately twice its weight of ethanol, into contactwith hydrogen in. the presence of a nickel-on-kieselguhr .hydrogenating catalyst at a temperature within the range of -180-200 C. and under a pressure of approximately 100-200 atmospheres.

13. As a new composition the hydrogenated phenol-ketone condensation product, boiling above C./2 mm. andcorresponding to the general formula HH X its or. g

15. As a new composition the hydrogenated di (4-hydroxy 3 methylphenyl) dimethylmethane product characterized by .the following properties: odorless, white, semi-plastic, B. P. C./1 mm., soluble in alcohols, insoluble in water and caustic alkalis. and corresponding to the following structural formula:

18. As a new composition the hydrogenated 1,1- diflehydroxypherrvl) cyclohexane product characterized by being an odorless, white solid, M. P. 220-240 C., insoluble in water and caustic alkalls, and soluble in hot alcohols, and corresponding to the'tollowing structural formula:

RAYMOND E. THOMAS.

white, tacky, semi-solid, plastic, B. P. 180- 

